|Publication number||US5332511 A|
|Application number||US 08/081,899|
|Publication date||Jul 26, 1994|
|Filing date||Jun 25, 1993|
|Priority date||Jun 25, 1993|
|Also published as||WO1995000445A1|
|Publication number||08081899, 081899, US 5332511 A, US 5332511A, US-A-5332511, US5332511 A, US5332511A|
|Inventors||Walter A. Gay, Bonnie B. Sandel, Jayne F. Carney|
|Original Assignee||Olin Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (19), Non-Patent Citations (11), Referenced by (96), Classifications (21), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1. Field of the Invention
The present invention relates to a process of sanitizing water in swimming pools, spas, and hot tubs wherein the level of bacteria is lowered. In particular, the present invention relates to a process of sanitizing by treating said water with a bactericidal effective amount of a combination of di-isodecyl dimethyl ammonium chloride and copper (II) ions and also treating said water at least intermittently with an oxidant selected from the group consisting of available chlorine, available bromine and ozone.
2. Brief Description of the Prior Art
Water in swimming pools, spas and hot tubs is constantly recirculated and fresh water is normally added only to maintain the desired volume. Although this water is usually filtered continuously to keep it free of suspended matter, it frequently contains bacteria. Treatment with one or more sanitizers to control the bacteria count is necessary.
Numerous chemical compounds have been reported for use in swimming pools, spas, and hot tubs. These chemicals include various quaternary ammonium salts, copper salts, and oxidants such as chlorine sources or bromine sources or ozone or peroxy compounds such as hydrogen peroxide and potassium peroxymonosulfate (OXONE). The use of combinations of such sanitizers is also known.
At the present time, the main disinfectant used in swimming pools, spas and hot tubs is chlorine. It is an effective bactericide, but suffers from two main disadvantages. One, at improper pH and concentration levels it may cause eye irritation. Two, it has to be added at frequent intervals to maintain an effective concentration for killing bacteria.
Ozone has also been used as a disinfectant for swimming pools, spas and hot tubs; but, it is limited to frequent or continuous dosing to maintain an effective concentration for killing bacteria. Such frequent or continuous treatments are required with ozone since there is at the present time no technology available for providing residual ozone. Also, if people come into contact with high concentrations of ozone, such as where the ozone is injected into the water, they may experience unpleasant headaches and the like.
Certain quaternary ammonium compounds have also been reported as being useful in swimming pools, spas, and hot tubs as bacteristats, bactericides, and algaecides. Those used as bacteristats and bactericides have required relatively high levels (e.g. over 100 ppm by weight) to give the rapid bacteria kill times needed for pool treatment. However, at such high concentration levels, quaternary ammonium salts in general have the potential of producing objectionable, aesthetically unpleasing turbid swimming pool water having a high total organic carbon (TOC) content. Furthermore, such high concentrations of quaternary ammonium salts may increase the likelihood of skin irritation of people using those bathing facilities.
Quaternary ammonium salts have also been used in swimming pools, spas and hot tubs as algaecides. For example, known commercial algaecide products include SUN® Algae Preventor (an alkyl dimethyl benzylammonium chloride) and HTH® Non-Foaming Algaecide Concentrate [poly[oxyethylene(dimethyliminio)ethylene(dimethyliminio)ethylene dichloride]]. Such algaecides are used in relatively low concentrations (under 10 ppm by weight). At such concentrations, these known quaternary ammonium algaecides generally do not provide the rapid kill times for swimming pools.
In practice, harmful bacteria must be killed rapidly if they are present in a swimming pool, spa or hot tub. Indeed, the standard test method for disinfectants in swimming pools [American Organization of Analytical Chemists (A.O.A.C.) test method 4.047 entitled "Disinfectants (Water) for Swimming Pools"] requires that a swimming pool bactericide kills high levels of bacteria in only 30 seconds of contact. With quaternary ammonium salts, this rapid bactericidal activity must be accomplished at low concentrations, e.g. 60 ppm or less, to avoid the potential of producing objectional, unpleasing turbid swimming pool water having a high total organic carbon (TOC) content as well as increasing the likelihood of skin irritation of people using these bathing facilities.
It is believed that the present invention represents a viable alternative to the above-noted problems with existing swimming pool, spa and hot tub bactericides.
Examples of references describing the use of individual quaternary ammonium compounds or other water-treatment bactericides or combinations of bactericides for water treatment and other applications include:
U.S. Pat. No. 3,510,424, which issued to Zumbrunn on May 5, 1970, teaches that inorganic and organic peroxoacids such as peroxosulfuric acid and its salts and peroxodisulfuric acid and its salts may be used to convert toxic cyanides in industrial effluent streams to nontoxic and hydrolysable cyanates.
U.S. Pat. No. 3,567,729, which issued to Lewis et al. on Mar. 2, 1971, teaches the use of certain quaternary ammonium salts as germicides.
U.S. Pat. No. 3,624,082, which issued to Lewis et al. on Nov. 30, 1971, teaches a process for making selected quaternary ammonium salts which may be useful as germicides.
U.S. Pat. No. 3,702,298, which issued to Zsoidos et al. on Nov. 7, 1972, teaches a method of treating swimming pools with a combination of a peroxy salt, such as salts of peroxymonosulfuric acid, and a copper salt.
U.S. Pat. No. 3,730,702, which issued to Shay et al. on May 1, 1973, teaches a method of inhibiting microorganisms by applying thereto selected water-soluble unsymmetrical di-higher alkyl dimethyl ammonium salts. This product may be used to disinfect hard surfaces, fabrics, topical portions of the body and water.
U.S. Pat. No. 3,733,420, which issued to Wakeman et al. on May 18, 1973, teaches a method of inhibiting microorganisms in hard water aqueous solutions [e.g., swimming pools (see col. 3, line 15)] using octyl dodecyl dimethyl ammonium salts. It is noted that this invention is stated to be useful for bactericidal purposes (see col. 4, line 11).
U.S. Pat. No. 3,845,216, which issued to Brink et al. on Oct. 29, 1974, teaches a method of controlling the growth of bacteria in aqueous systems by contacting the system with a combination of B-bromo-B-nitrostyrene and didecyldimethyl ammonium chloride.
U.S. Pat. No. 4,098,602, which issued to Seymour et al. on Jul. 4, 1978, teaches an algicidal composition comprising selected ammonium quaternary compounds and a copper complex formed by reacting a water insoluble copper compound and alkanol amines.
U.S. Pat. No. 4,311,598, which issued to Verachtert on Jan. 19, 1982, describes a process for the disinfection of a bacteria-containing aqueous medium by contacting that medium with a combination of hydrogen peroxide or peroxyacid, a soluble copper salt and an autoxidisable reducing agent (e.g., 1,2,3-trihydroxybenzene, benzaldehyde, dihydroxyfumaric acid, malonic acid, ascorbic acid, or an alkali metal sulfate.
U.S. Pat. No. 4,450,174, which issued to Green et al. on May 22, 1984, describes the use of di-n-decyl dimethyl quaternary ammonium salts to inhibit bacteria in aqueous systems.
U.S. Pat. No. 4,594,091, which issued to Givan on Jun. 10, 1986, is directed to the use of certain boron derivatives to inhibit algal and fungal growth in water.
U.S. Pat. No. 4,790,940, which issued to Costaldi et al. on Dec. 13, 1988, teaches a process for the treatment of free cyanide-containing wastewater to destroy the free cyanide content thereof by treating said waters under alkaline conditions with polysulfide in the presence of a cationic surfactant catalyst (e.g., dialkyldimethyl quaternary ammonium salt).
U.S. Pat. No. 4,923,619, which issued to Legros on May 8, 1990, teaches the treatment of water of swimming pools and industrial water by means of a combination of (a) quaternary ammonium salts and (b) water-soluble copper and/or silver salts and peroxide compounds releasing oxygen, such as monopersulfate or peroxidisulfate of potassium. See col. 1 of this patent.
U.S. Pat. No. 4,952,398, which issued to Tapin on Aug. 28, 1990, teaches the treatment of swimming pool water using the combination of a quaternary ammonium compound and a copper salt as a biocide.
U.S. Pat. No. 5,131,938, which issued to Girvan on Jul. 21, 1992, suggests that certain boron derivatives may be used for killing algae and fungus in swimming pools. This patent further teaches that these boron derivatives may be used with known pool sanitizers (e.g., halogens, copper, hydrogen oxide, ozone, oxone, and quaternary ammonium compounds). See col. 5 of this patent.
U.S. Pat. No. 5,149,354, which issued to Delaney on Sep. 22, 1992, suggests a composition to inhibit the growth of algae, fungi, and bacteria, and to prevent the formation of turbidity in pool water comprising certain amounts of (a) copper sulfate, (b) silver nitrate, (c) sodium gluconate, (d) zinc chloride or zinc sulfate, (e) water, and (f) a complexone capable of forming water-soluble copper complexes (e.g., EDTA or a suitable alkali metal salt thereof).
United Kingdom Pat. Application 2,194,227, filed by Crystalclear S. A. and published on Mar. 2, 1988, teaches treating a body of water, such as a swimming pool, by adding thereto a liquid component and an oxidizing component. The liquid component comprises a polymeric cationic quaternary ammonium compound, a sequestering agent, and a copper salt. The oxidizing component may include sodium perborate, potassium persulfate, an alkali or alkaline earth hypochlorite, a trichloroisocyanurate, or an alkali metal dichloroisocyanurate.
European Pat. No. 59,978, which was granted to Bayrol on Jun. 13, 1984, claims a process for the disinfection of water and the oxidative decomposition of oxidizable impurities contained in the water by adding to the water the combination of (a) quaternary ammonium compounds, (b) water-soluble copper salts and or silver salts, and (c) an oxygen-liberating peroxide compound (e.g., potassium hydrogen monopersulfate).
European Pat. Application No. 0286453, which was filed by Pernox Manufacturing Company and published on Oct. 12, 1988, describes a biocidal composition for the treatment of water comprising certain quaternary ammonium compounds together with copper cations and/or a biocide containing a gem. halonitromethylene group.
G. R. Bhat et al. "The Green Hair Problem: A Preliminary Investigation", J. Soc. Cosmet. Chem. Vol. 30, 1-8 (January/February 1979) suggests that the combination of copper and peroxide enhances the phenomenon of blond hair acquiring a green tint. The experiments in this paper included a test where the blond hair was oxidized with hydrogen peroxide and immersed in a commercial formulation of a quaternary ammonium compound (distearyl dimethyl ammonium chloride).
L. K. Landeen et al. "Efficacy of Copper and Silver Ions and Reduced Levels of Free Chlorine in Inactivation of Legionella Pneumophila", Applied and Environmental Microbiology, Dec. 1989 pages 3045-3050, describes the activity of copper and silver ions in the presence of low levels of free chlorine against Legionella pneumophila.
M. T. Yahya "Disinfection of Bacteria in Water Systems by using Electrolytically Generated Copper:Silver and Reduced Levels of Free chlorine", Con. J. Microbiol. Vol. 36, pages 109-116, 1990, describes the activity of copper or silver ions with low levels of free chlorine against various bacteria in water.
G. P. Fitzgerald "Compatibility of Swimming Pool Algicides and Bactericides, Water & Sewage Works," vol. 115(2), pages 65-71 (1968), teaches that various amines, quaternary ammonium compounds, copper and silver salts have algistatic, algicidal, and bactericidal properties in swimming pools.
U.S. EPA Freedom of Information Request RIN-5973-92 shows that Bio-Guard MSA Algicide made by Bio-Lab, Inc. of Decatur, Ga. in 1974 contained the combination of copper and a quaternary ammonium compound (dimethyl dichlorobenzyl ammonium chloride).
Separately, di-isodecyl dimethyl ammonium chloride (sold commercially as BTC-99, by Stepan Co.) has been reported as having several uses.
Stepan Product Bulletin for BTC-99 (copyright 1990) states BTC-99 is useful as a microbiocide for swimming pool and cooling water treatment applications. A typical maintenance dose for a swimming pool is 3 oz. per 20,000 gallons. This brochure states that BTC-99 has demonstrated complete destruction of various algae including Green Algae, Square D Algae, Blue-Green Algae, and Black Algae.
Accordingly, the present invention is directed to a process for sanitizing water in swimming pools, spas and hot tubs whereby the level of bacteria in said water is lowered comprising:
treating said water with a bactericidal effective amount of a combination of di-isodecyl dimethyl ammonium chloride and copper (II) ions, the concentration of di-isodecyl dimethyl ammonium chloride in said water being less than 60 parts per million parts of water (60 ppm) by weight; and
treating said water at least intermittently with an oxidant selected from the group consisting of available chlorine, available bromine, and ozone.
The quaternary ammonium salt employed in the present invention, di-isodecyl dimethyl ammonium chloride, is a commercially available algaecide sold under the name BTC-99 by Stepan Chemical Co. of Northfield, Ill. Its Chemical Abstract Number (CAS) is 91490-94-7, and it is also known as isodecanamimium, N-isodecyl-N,N-dimethyl, chloride.
Various preparations of di-isodecyl dimethyl ammonium chloride are suggested in U.S. Pat. No. 4,444,790, which issued to Green et al. on Apr. 24, 1984.
The source of copper (II) ions used in the present invention may be any source of copper (II) cations including any water-soluble copper (II) salts which have a biocidally acceptable anion, which is capable of solubilizing copper (II) cations in water and is compatible with the above-noted quaternary ammonium salt. Examples of such copper (II) sources include copper (II) carbonate, copper (II) benzoate, copper (II) bicarbonate, copper (II) chloride, copper (II) sulfate, copper (II) bromide, copper (II) acetate, copper (II) formate, copper (II) trichloroacetate, copper (II) triethanolamine complex, copper (II) ethylenediamine tetraacetic acid complex, copper (II) citrate, copper (II) gluconate, and mixtures thereof. Copper (II) sources would also include any device, compound, or process which generates copper (II) ions in water. The preferred source of said copper (II) ions is copper (II) sulfate.
The present application recites "a bactericidal effective amount of the combination" of this quaternary ammonium salt and copper (II) ions. This term, as used in the present specification and claims, means any total amount of these two components which results in an effective bactericidal activity against at least 99.9% preferably 99.99% of bacteria initially present in the water treated with this combination.
In other words, if a body of water containing one million colony forming units (CFU's) of bacteria per milliliter was treated in accordance with the present invention, then less than 1,000 colony forming units (CFU's) will be left per milliliter of water after contact with this combination. Preferably, it is also desired that this amount of this combination be sufficient to cause a rapid decrease or lowering of the bacteria within about 60 seconds from contact, more preferably within about 30 seconds, so as to meet the requirements of the above-noted standard test method for disinfectants in swimming pools (A.O.A.C. Test Method 4.047).
The preferred weight ratio of the quaternary ammonium salt to the copper (II) ion source is from 3:1 to 600:1, more preferably, from about 30:1 to about 300:1, most preferably, from about 60:1 to about 150:1.
The quaternary ammonium salt and copper (II) ion source may be combined in any conventional way. Preferably, it may be desirable to simply mix them together for later addition to a swimming pool, spa or hot tub.
Other conventional water-treatment chemicals may be contained with these two critical chemicals. Such conventional chemicals may include defoamers, perfumes, insect repellants, flocculants, dyes, colorants, and sequestering agents.
Alternatively, the di-isodecyl dimethyl ammonium chloride and copper (II) ion source may be added individually to the water of the swimming pool, spa or hot tub. Such additions may be simultaneously or at different times. If the latter method is employed, such additions of second component are preferably made before the concentration of the first component becomes negligible (i.e., less then 0.01 ppm).
It should be noted that the maximum concentration of di-isodecyl dimethyl ammonium chloride in the water being treated should be about 60 ppm by weight. This maximum limit is necessary to avoid the potential of producing objectionable, aesthetically unpleasing turbid water having a high total organic carbon (TOC) content and to decrease the likelihood of any skin irritation of bathers using these facilities. The preferred concentration of this quaternary ammonium salt in the water is from about 5-40 ppm by weight. It is also preferred that the concentration of the copper (II) ion in the water be from about 0.1-2 ppm by weight, more preferably about 0.5-1 ppm by weight. These levels are desired to cause a decrease of at least 99.9%, preferably 99.99% , of bacteria in the water, more preferably, within 30 seconds.
In the present invention, a pool operator would only want to dissolve the quaternary ammonium compound and copper (II) ion source in the water being treated and ensure that a uniform concentration of each in the above ranges is achieved.
Depending upon the particular aqueous medium being treated and upon various external factors, redosing of the quaternary ammonium salt and copper (II) ions may be necessary. For example, a heavily used swimming pool may require redosing at more frequent intervals than another pool of the same size which was used only occasionally or lightly. Redosing of the quaternary ammonium salt and copper (II) ion source may be carried out together or individually. Pool operators may use standard testing kits to determine the concentration of each component and whether or not (and how much) redosing is needed.
A critical feature of the present invention is to add at least intermittently an oxidant selected from the group consisting of available chlorine, available bromine, and ozone to the water along with the combination of the quaternary ammonium salt and copper (II) ions. The terms "available chlorine" and "available bromine" as used in the present specification and claims are intended to mean positive chlorine and positive bromine as it is well known in this art. Available chlorine sources include chlorine (Cl2) calcium hypochlorite, chlorinated isocyanurates, chlorinated glycolurils, chlorinated hydantoins, chlorinated imidazolidinones, chlorinated oxazolidinones, chlorinated amines and mixtures thereof.
Available bromine sources include liquid bromine, nitrogen-bound bromine such as the bromohydantoins (e.g., 1-bromo-3-chloro-5,5-dimethylhydantoin), bromide ion combined with oxidizers such as ozone, potassium monoperoxysulfate, or a chlorine source and bromide ion converted by electrolytic generation.
Ozone sources include ozone which is generated from oxygen or air through use of a corona discharge generator or a UV light generator (photolytically).
Generally, it is desired to add the oxidant source at intervals to effect a "shock treatment" on the body of water being treated. The desired concentration of available chlorine being added will depend upon the particular available chlorine source chemical being employed and the specific application required. Usually, it is desirable to add about 0.5 to about 30 ppm, more preferably, about 2-15 ppm by weight of available chlorine to the water at least once every thirty days, preferably at least once every 4-10 days.
The desired concentration of available bromine being added is similar to that of available chlorine. More preferably, one would add about 0.5 ppm to about 30 ppm, most preferably about 2-15 ppm, of available bromine to the water at least once every 30 days, preferably at least once every 4-10 days.
The desired concentration of ozone being added should be such that the ozone level in the water will meet the required oxidant demand for that particular application. Generally, that minimum amount of ozone added is sufficient to result in at least 0.1 mg/liter residual ozone at the discharge into the pool. The preferred amount of ozone generated may be controlled and monitored at the outlet of the ozone contact chamber by means of redox potential (oxidation-reduction potential in North America=ORP), rather than by monitoring for residual ozone. Pools and spas which use ozone alone are generally maintained at ORP level of 720±20 mV. This normal level may change because of the amount of oxidizable material in the water. The preferred maximum level of ozone addition should be less than that which would cause discomfort to humans.
By practice of the present invention, one is able to rapidly and economically sanitize water in swimming pools, spas and hot tubs to safe and acceptable bacteria levels. Furthermore, at the very low concentrations found to be effective, the particular quaternary ammonium compound is believed to have no effect on the eyes, no significant objectionable odor or taste, and does not significantly bleach clothing as may happen with the use of chlorine or ozone. Furthermore, this invention is believed effective against bacteria resistant to the use of di-isodecyl dimethyl ammonium chloride or copper (II) ions alone or the combination thereof.
Still further, this invention is believed effective against bacteria resistant to the use of di-isodecyl dimethyl ammonium chloride or chlorine shock or the combination thereof. In other words, prolonged treatment of water in a swimming pool, spa, or hot tub with only one or any two of three components of the present invention may result in the growth of resistant bacteria whereas the use of all three components of the present invention would prevent the development of such resistant bacteria. The use of this particular quaternary ammonium salt in the present invention causes little foaming and results in clear water compared to many other quaternary ammonium salts.
The following experiments are provided to better understand the present invention. All parts and percentages are by weight except where explicitly stated otherwise. All temperatures are degrees Celsius (°C.) except where explicitly stated otherwise.
E. coli, ATCC 11229, were grown on tryptic soy agar slants for 18 to 24 hours at 35° C. The slants were then washed with 10 ml of sterile saline (0.85% by weight NaCl) and centrifuged at 10,000 revolutions per minute for 10 minutes. The supernatant was discarded, and the culture resuspended in 10 ml of sterile saline (0.85%). The centrifugation and removal-of-supernatant steps were repeated two times. The culture was then resuspended in sterile reverse osmosis water, and the culture suspension adjusted to an optical density of 0.2 at 550 nm using a Bausch & Lomb colormeter, Model No. 20. The final culture suspension has approximately 200,000,000 viable cells per milliliter, i.e., 200,000,000 colony forming units/ml or 200,000,000 cfu/ml.
The test used herein as a standard to verify and demonstrate the bactericidal activity of the present invention is a variation of the American Organization of Analytical Chemists (A.O.A.C.) procedure 4.047 entitled "Disinfectants (Water) for Swimming Pools". The variation, which makes the test more stringent, consists of using dechlorinated tapwater, having an alkalinity of 100 ppm and a calcium hardness of 90-100 ppm. The quaternary ammonium salt solutions were prepared at the use concentrations given in Table I at pH 7.5. A stock copper (II) solution was prepared at 100-fold the test concentration from copper sulfate pentahydrate at pH 5.5. A stock oxidizer solution was prepared at 100 times the test concentration from OXONE potassium peroxymonosulfate with the solution having a pH of 7.5.
The quaternary ammonium salt, copper (II), and OXONE potassium peroxymonosulfate were evaluated at the concentrations set forth in Table I either by themselves or in the indicated combinations. For tests involving individual components, 10 ml of the appropriate solution or sterile reverse osmosis water were added aseptically to sterile, capped culture tubes. For tests involving combinations of ingredients, 10 ml of the quaternary ammonium salt solutions were added aseptically to sterile, capped culture tubes and an appropriate volume of copper (II) or the OXONE monopersulfate compound stock solution added less than 5 minutes before the addition of the culture suspension to start the timed exposure.
To the above-described test solutions, at room temperature, 50 microliters of bacterial suspension were added, and the time-of-addition recorded as zero time. Immediately after adding the bacteria suspension, the reaction mixture was vortexed for 10 seconds, and 1 milliliter samples taken at times shown in Table I. Just prior to sampling, the vortexing procedure was repeated. Each 1 milliliter sample was added immediately to 9 ml of a neutralizer. The neutralizer (pH of 7.5) was made by combining (a) 33.4 milliliters of an aqueous solution containing 4% by weight azolectin and 28% by weight TWEEN® 80; (b) 8.33 milliliters of a standard phosphate buffer; and (c) 558.33 milliliters of distilled water to make a 600 milliliter stock neutralizer solution. This solution was autoclaved for 20 minutes at 121° C. to kill any organisms therein. A second stock neutralizer solution was similarly prepared for those tests in which copper (II) was or OXONE would be present. This second neutralizer stock was prepared the same way except 0.6 grams of sodium thiosulfate and 0.6 grams of sodium thioglycolate were added to the 600 milliliter solution before autoclaving. Controls were run to insure that compounds are effectively neutralized. About 1,000,000 cfu/ml of the test bacteria were exposed to each test solutions.
After neutralization at the selected time-of-contact, 1 milliliter portions of the neutralized samples were added to plastic petri dishes, and tempered tryptone glucose extract agar added to each plate. The plates were then incubated at 37° C. for about hours and colonies were counted. The numbers are then corrected to cfu/ml by applying the appropriate dilution factor used.
TABLE I______________________________________LAB TEST vs. E. COLI BACTERIA E. COLI REMAININGBTC-99** OXONE CU.sup.+2 (cfu/ml)*(ppm) (ppm) (ppm) 0.5 min. 5.0 min.______________________________________40 0 0 1925 35020 0 0 >3000 28010 0 0 >3000 >3000 0 12 0 >3000 >3000 0 24 0 >3000 >3000 0 0 1 >3000 >3000 0 24 1 >3000 >300020 0 1 >3000 >300020 12 0 >3000 140020 12 1 >3000 >300010 0 0.5 >3000 >300010 12 0 >3000 >300010 12 0.5 >3000 >3000______________________________________ *At "0" time, approximately 1,000,000 cfu/ml **ppm of active ingredient
TABLE I shows the laboratory data for testing di-isodecyl dimethyl ammonium chloride at 10 to 40 ppm active ingredient as a potential sanitizer in a swimming pool, hot tub, or spa. By itself, this quaternary ammonium salt is completely ineffective at 10 ppm, even after a 5-minute contact-time. At 20 ppm, efficacy is poor at 30-seconds contact-time, and a significant number of bacteria survivors is left after 5 minutes contact-time. At 40 ppm, bactericidal efficacy is only 99.8% at a 30-second contact-time. Thus, it is concluded that di-isodecyl dimethyl ammonium chloride is ineffective by itself for use as sanitizer for these applications.
Also shown is the laboratory data for testing the swimming pool, hot tub, and spa shock-treatment oxidant, OXONE potassium peroxymonosulfate compound at 12 and 24 ppm, and for testing copper (II) at 1 ppm. By themselves, neither is an effective bactericide.
Combining copper (II) and OXONE does not improve the bactericidal efficacy. Combining di-isodecyl dimethyl ammonium chloride with either copper (II) or OXONE or a mixture of copper (II) and OXONE was found to actually decrease the bactericidal activity as compared to using only di-isodecyl dimethyl ammonium chloride. Thus, it is concluded that combinations of this quaternary ammonium salt with copper (II) and/or an OXONE shock treatment is ineffective for use as a sanitizer for these applications.
Comparative test were performed in pools having a water capacity of about 2,100 gallons. The pools were filled with water and the alkalinity adjusted to about 100 ppm, and the calcium hardness adjusted to about 200 ppm using standard swimming pool chemicals. The pH was adjusted to about 7.5 initially and maintained at pH 7-8. Each swimming pool was equipped with a standard sand filter through which the pool water circulated for 8 hours per day. Bacteria counts were determined by standard methods using 2 and/or 7-day incubation times.
To the above-described pool 1 was added 688 ml of BTC-99, corresponding to a swimming pool concentration of 40 ppm di-isodecyl dimethyl ammonium chloride. OXONE potassium peroxymonosulfate compound was added at 12 ppm as an oxidant shock treatment. A protocol was followed so that the quaternary ammonium salt concentration was maintained at 30-40 ppm for the test duration. An algae suspension containing about 6 billion associated bacteria cells was added on days 6, 13, 20, and 27 after collecting a water sample for determining bacteria counts. OXONE potassium peroxymonosulfate compound was added at 21 ppm on days 8, 15, and 22. A synthetic bather load was added 5 days a week to simulate typical compounds introduced to a pool from bathers.
TABLE II shows bacteria counts at various times during the 1-month test for this system. As predicted from the laboratory tests, the use of di-isodecyl dimethyl ammonium chloride with an oxidant shock treatment of OXONE potassium peroxymonosulfate compound failed to effectively prevent the growth of bacteria.
TABLE II______________________________________DI-ISODECYL DIMETHYL AMMONIUM CHLORIDE/OXONE; SWIMMING POOL TEST SYSTEM-1 BACTERIA COUNTS (cfu/ml)DAY 2 DAYS 7 DAYS______________________________________ 1 0 -- 2 0 0 6 610 510 7 7500 8900 9 -- 013 32 3414 120,000 120,00016 -- 020 -- 5421 -- 83,00023 -- 027 21,000 --28 820,000 760,000______________________________________
This test was performed analogously to that described in Section II-B, with the exception that the initial and weekly oxidant shock treatment employed 7.5 ppm free available chlorine using 65% calcium hypochlorite. Oxidant was added on days 8, 15, 22 and 29; algae, on days 6, 13, 20, 27 and 34; synthetic bather load, 5 days a week.
Table III shows bacteria counts at various times during the 35-day test. Relatively low bacteria counts were found up to day 28, at which time a high bacteria count of about 735 cfu/ml was recorded. By day 34 the bacteria count, before algae/bacteria addition, had increased to 12,000 cfu/ml. Thus, as is obvious, di-isodecyl dimethyl ammonium chloride with an oxidant shock treatment of free available chlorine failed to effectively prevent the growth of bacteria.
TABLE III______________________________________DI-ISODECYL DIMETHYL AMMONIUM CHLORIDE/CHLORINE; SWIMMING POOL TEST SYSTEM-2 BACTERIA COUNTS (cfu/ml)DAY 2 DAYS 7 DAYS______________________________________ 1 0 0 2 0 0 6 0 2 7 9 14 9 -- 013 0 014 13 1616 -- 020 -- 5421 -- 2223 -- 027 69 4828 760 71030 -- 034 12,000 --35 7,200 --______________________________________
On day 29 Pool Test 1, described in Section II-B, was modified to Pool Test 1a by using an oxidant shock treatment of 7.5 ppm free available chlorine in place of the OXONE potassium peroxymonosulfate compound shock treatment. On day 30, the bacteria count was 0 cfu/ml, but by day 34, the bacteria count had increased to 1,100,000 cfu/ml. The algae suspension containing bacteria was added on day 34, and on day 35 a bacteria count of 3,100,000 cfu/ml was found. These data confirmed the ineffectiveness of a di-isodecyl dimethyl ammonium chloride/chlorine system for controlling bacteria, as concluded by the test described in Section II-C.
On day 36, pools 1a and 2, were oxidant shock treated with 15 ppm free available chlorine. On day 38, bacteria counts in both pools were <1 cfu/ml, and 1 ppm copper (II) was added to pool 1; no copper (II) was added to pool 2. On day 42, the bacteria count in the copper (II) treated pool 1a was 15 cfu/ml, but was 4500 cfu/ml in pool 2 that was not treated with copper (II). It is thus obvious that effective bacteria control was achieved by using a di-isodecyl dimethyl ammonium chloride/copper (II) system with a chlorine oxidant shock treatment.
Additional confirmation of the exceptional bactericidal efficacy of this system was found by removing a sample of pool water on day 36 from pool 2, prior to shock treatment, and adding 1 ppm copper (II) to it. At the start of this confirmation test the bacteria count was 22,000 cfu/ml; 90 minutes after contact with the copper (II), the bacteria count had dropped to the detection limit of less than 1 cfu/ml.
To test pool 4, as described in Section II-A, was added 344 ml of BTC-99, corresponding to a swimming pool concentration of 20 ppm di-isodecyl dimethyl ammonium chloride. This was followed by the addition of 170 ml of an 18% copper sulfate pentahydrate solution, corresponding to 1 ppm copper (II) in the swimming pool. OXONE potassium peroxymonosulfate compound was added at 12 ppm as an oxidant shock treatment on Day 8. Bacteria counts were monitored for 33 days from the initial charge of the quaternary ammonium salt, which was periodically added to maintain a concentration of about 20 ppm. The highest count was only 29 cfu/ml during this time.
On day 34, an algae suspension containing bacteria (approximately 25 billion cells) was added. This addition was repeated every 7 days for the duration of the test. On day 36, 12 ppm OXONE potassium peroxymonosulfate compound was added. This addition was repeated every 7 days to day 71, at which time the addition of 24 ppm OXONE potassium peroxymonosulfate compound every 7 days commenced. A synthetic bather load was added 5 times a week starting on day 34 of the test.
TABLE IV shows the bacteria counts at various times during the 83-day test. As predicted from the laboratory tests, the use of di-isodecyl dimethyl ammonium chloride with copper (II) and OXONE potassium peroxymonosulfate compound oxidant shock treatment failed to effectively control the growth of bacteria.
TABLE IV______________________________________DI-ISODECYL DIMETHYL AMMONIUM CHLORIDE/COPPER (II)/OXONE;SWIMMING POOL TEST SYSTEM-4 BACTERIA COUNTS (cfu/ml)DAY 2 DAYS 7 DAYS______________________________________ 1 -- 0 2 -- 0 7 -- 114 0 2921 -- 028 -- 430 -- 035 -- 1342 -- 58044 -- 149 -- 160051 -- 356 -- >300057 470,000 560,00058 0 059 1000 69062 10,000 10,00069 1,200 1,00071 -- 31,00076 136 13977 4,500 5,70078 140,000 130,00079 0 080 3 483 20,000 20,000______________________________________
Laboratory tests using di-isodecyl dimethyl ammonium chloride lead one to conclude that this compound is an ineffective bactericide for use as a sanitizer in swimming pools, hot tubs, and spas when used alone, or in combination with copper (II) or an oxidant shock treatment. This general conclusion was confirmed by tests in swimming pools, with the unexpected exception that, when di-isodecyl dimethyl ammonium chloride was used with copper (II) in conjunction with chlorine as an oxidant shock treatment, a superior sanitizing system resulted as compared to the use of a similar system with OXONE potassium peroxymonosulfate compound for oxidant shock treatment.
While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications, and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents, and other publications cited herein are incorporated by reference in their entirety.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3567729 *||Jan 12, 1968||Mar 2, 1971||Swift & Co||Diquaternary ammonium halides|
|US3624082 *||May 26, 1966||Nov 30, 1971||Swift & Co||Process for making 2-hydroxy-3-alkoxy quaternary ammonium propane salts|
|US3702298 *||Sep 10, 1970||Nov 7, 1972||Eco Sciences Inc||Method of disinfecting with divalent and trivalent metal germicide|
|US3730702 *||Jun 9, 1971||May 1, 1973||Millmaster Onyx Corp||Biocidal unsymmetrical di-higher alkyl dimethyl ammonium compounds|
|US3733420 *||Mar 26, 1971||May 15, 1973||Millmaster Onyx Corp||Biocidal octyldodecyl dimethyl ammonium compounds in hard water solutions|
|US3845216 *||Aug 11, 1972||Oct 29, 1974||Betz Laboratories||Slime control composition containing quaternary ammonium chloride and its use|
|US4098602 *||Jun 28, 1976||Jul 4, 1978||Applied Biochemists, Inc.||Algaecidal composition|
|US4450174 *||May 27, 1982||May 22, 1984||Millmaster Onyx Group, Inc.||Decyl quaternary ammonium compounds|
|US4569800 *||Jul 21, 1983||Feb 11, 1986||Akzona Incorporated||Quaternary ammonium salts useful as fabric softeners|
|US4746368 *||Feb 28, 1986||May 24, 1988||Akzo America Inc.||Decolorization of aqueous saccharide solutions and sorbents therefor|
|US4806520 *||Mar 23, 1988||Feb 21, 1989||Akzo America Inc.||Decolorization of aqueous saccharide solutions and sorbents therefor|
|US4923619 *||Oct 14, 1986||May 8, 1990||Fabricom Air Conditioning S.A.||Disinfectant compositions and disinfection process applicable to infected liquids or surfaces|
|US4952398 *||Mar 17, 1988||Aug 28, 1990||Jean Tapin||Biocidal composition with copper algicide|
|US5080830 *||Apr 26, 1990||Jan 14, 1992||Akzo N.V.||Water-dispersible compositions comprised of quaternary ammonium compounds|
|US5131938 *||Sep 16, 1991||Jul 21, 1992||Girvan John W||Borate algaecide and fungicide|
|US5149354 *||Jan 10, 1991||Sep 22, 1992||Delaney Brendan J||Composition for treating swimming pools|
|EP0059978B1 *||Mar 9, 1982||Jun 13, 1984||BAYROL Chemische Fabrik G.m.b.H.||Process for the chemical treatment and disinfection of waters and aqueous systems|
|EP0286453A2 *||Apr 11, 1988||Oct 12, 1988||Advanced Chemical Products Limited||Biocide|
|GB2194227A *||Title not available|
|1||*||AKZO Product Bulletin for ARQUAD HTL8 (1990).|
|2||G. R. Bhat et al., "The Green Hair Problem: A Preliminary Investigation" J. Soc. Cosmet. Chem. 30 (Jan./Feb., 1979) (C.A. 90(20):156982r).|
|3||*||G. R. Bhat et al., The Green Hair Problem: A Preliminary Investigation J. Soc. Cosmet. Chem. 30 (Jan./Feb., 1979) (C.A. 90(20):156982r).|
|4||George P. Fitzgerald, "Compatibility of Swimming Pool Algicides and Bactericides", Water & Sewage Works, vol. 115(2), pp. 65-71 (1968) Federal Register vol. 56, #168, pp. 42,685-42,687, Aug. 29, 1991.|
|5||*||George P. Fitzgerald, Compatibility of Swimming Pool Algicides and Bactericides , Water & Sewage Works, vol. 115(2), pp. 65 71 (1968) Federal Register vol. 56, 168, pp. 42,685 42,687, Aug. 29, 1991.|
|6||Landeen et al., "Efficacy of Copper and Silver Ions and Reduced Levels of Free Chlorine in Inactivation of Legionella Pneumophila"; Applied & Environmental Microbiology, vol. 50, No. 12, Dec., 1989, pp. 3045-3050.|
|7||*||Landeen et al., Efficacy of Copper and Silver Ions and Reduced Levels of Free Chlorine in Inactivation of Legionella Pneumophila ; Applied & Environmental Microbiology, vol. 50, No. 12, Dec., 1989, pp. 3045 3050.|
|8||*||Stepan Product Bulletin for PTC 99 (1990).|
|9||Stepan Product Bulletin for PTC-99 (1990).|
|10||Yahya et al., "Disinfection of Bacteria in Water Systems by Using Electrolytically Generated Copper:Silver & Reduced Levels of Free Chlorine", Can. J. Microbiol. vol. 36, pp. 109-116 (1990).|
|11||*||Yahya et al., Disinfection of Bacteria in Water Systems by Using Electrolytically Generated Copper:Silver & Reduced Levels of Free Chlorine , Can. J. Microbiol. vol. 36, pp. 109 116 (1990).|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5645608||Apr 17, 1996||Jul 8, 1997||Cooper; Theodore R.||Cold water wash method|
|US5670059 *||Sep 20, 1995||Sep 23, 1997||Bio-Lab, Inc.||Method and compositions for treating recirculating water systems|
|US5763382||Jan 3, 1996||Jun 9, 1998||Cyclo3Pss Textile Systems, Inc.||Cold water wash formula|
|US5766456 *||Jul 2, 1996||Jun 16, 1998||Fountainhead Technologies, Inc.||Water purifer for a pool|
|US5779913 *||Aug 1, 1996||Jul 14, 1998||Fountainhead Technologies, Inc.||Water purifier for a spa|
|US5780064 *||Sep 12, 1997||Jul 14, 1998||Babson Bros. Co.||Germicidal compositions for the treatment of animal infectious diseases of the hoof|
|US5888428 *||Sep 30, 1996||Mar 30, 1999||Great Lakes Chemical Corporation||Methods for generating residual disinfectants during the ozonization of water|
|US5916379 *||Feb 4, 1997||Jun 29, 1999||Abbey Research & Development Ltd.||Treatment of ferrous metal surfaces|
|US6006387||Nov 30, 1995||Dec 28, 1999||Cyclo3Pss Textile Systems, Inc.||Cold water ozone disinfection|
|US6019893 *||Jun 30, 1998||Feb 1, 2000||Fountainhead Technologies, Inc.||Water purifier for a spa|
|US6093422 *||Jun 16, 1998||Jul 25, 2000||Zodiac Pool Care, Inc.||Biocidal compositions for treating water|
|US6115862||Dec 27, 1999||Sep 12, 2000||Cyclo3Pss Textile Systems, Inc.||Cold water ozone disinfection|
|US6120698 *||May 15, 1998||Sep 19, 2000||Advanced Water Technology, Inc.||Balanced water purification composition|
|US6132629 *||Feb 3, 1999||Oct 17, 2000||Roger J. Boley||Method and apparatus for continuous or intermittent supply of ozonated water|
|US6143184 *||Mar 2, 1999||Nov 7, 2000||United States Filter Corporation||Air and water purification using continuous breakpoint halogenation|
|US6149819 *||Mar 2, 1999||Nov 21, 2000||United States Filter Corporation||Air and water purification using continuous breakpoint halogenation and peroxygenation|
|US6149821 *||Oct 23, 1998||Nov 21, 2000||Advanced Water Technology, Inc.||Balanced water purification system|
|US6165358 *||Jul 26, 1999||Dec 26, 2000||Zodiac Pool Care, Inc.||Water purifier for a spa|
|US6197814||Oct 9, 1998||Mar 6, 2001||Nvid International, Inc.||Disinfectant and method of making|
|US6217780||Dec 28, 1999||Apr 17, 2001||Zodiac Pool Care, Inc.||Biocidal compositions for treating water|
|US6387415 *||Apr 1, 1998||May 14, 2002||Bio-Lab, Inc.||Sequestered metal biocides using ionic polymeric stabilizing agents|
|US6409926 *||Nov 6, 2000||Jun 25, 2002||United States Filter Corporation||Air and water purification using continuous breakpoint halogenation and peroxygenation|
|US6419817||Jun 22, 2000||Jul 16, 2002||United States Filter Corporation||Dynamic optimization of chemical additives in a water treatment system|
|US6423234 *||Nov 6, 2000||Jul 23, 2002||United States Filter Corporation||Air and water purification using continuous breakpoint halogenation|
|US6458398||Sep 22, 2000||Oct 1, 2002||Eco Pure Food Safety Systems, Inc.||Cold water disinfection of foods|
|US6562243 *||Apr 5, 2001||May 13, 2003||Jonathan Sherman||Synergistic combination of metal ions with an oxidizing agent and algaecide to reduce both required oxidizing agent and microbial sensitivity to fluctuations in oxidizing agent concentration, particularly for swimming pools|
|US6583176 *||Mar 2, 2001||Jun 24, 2003||Innovative Medical Services||Aqueous disinfectant|
|US6620315||Feb 9, 2001||Sep 16, 2003||United States Filter Corporation||System for optimized control of multiple oxidizer feedstreams|
|US6623647||Mar 15, 2002||Sep 23, 2003||United States Filter Corporation||Methods of optimized control of multiple oxidizer feedstreams|
|US6645400||Dec 10, 2001||Nov 11, 2003||United States Filter Corporation||Corrosion control utilizing a hydrogen peroxide donor|
|US6716359||Aug 29, 2000||Apr 6, 2004||United States Filter Corporation||Enhanced time-based proportional control|
|US6776926||Aug 9, 2001||Aug 17, 2004||United States Filter Corporation||Calcium hypochlorite of reduced reactivity|
|US6890953||Mar 20, 2002||May 10, 2005||Innovative Medical Services||Process for treating water|
|US6991735||Feb 26, 2002||Jan 31, 2006||Usfilter Corporation||Free radical generator and method|
|US7108781||Feb 26, 2002||Sep 19, 2006||Usfilter Corporation||Enhanced air and water purification using continuous breakpoint halogenation with free oxygen radicals|
|US7203977||Aug 26, 2005||Apr 17, 2007||Roy W. Mattson, Jr.||Fill and drain jetted hydromassage antimicrobial water vessel|
|US7261905||May 9, 2003||Aug 28, 2007||Pure Bioscience||Disinfectant and method of making|
|US7285223||Oct 22, 2004||Oct 23, 2007||Siemens Water Technologies Holding Corp.||Enhanced air and water purification using continuous breakpoint halogenation with free oxygen radicals|
|US7435438||Feb 16, 2005||Oct 14, 2008||Pure Bioscience||Disinfectant and method of use|
|US7468135||Sep 4, 2007||Dec 23, 2008||Engineered Solutions, Inc.||Portable tank wastewater treatment system and method|
|US7601755||May 9, 2005||Oct 13, 2009||Pure Bioscience||Process for treating water|
|US7718067||May 19, 2005||May 18, 2010||Aero-Stream, Llc||Septic system remediation method and apparatus|
|US7732486||Mar 27, 2007||Jun 8, 2010||Pure Bioscience||Anhydrous silver dihydrogen citrate compositions|
|US7763297||Sep 4, 2008||Jul 27, 2010||Pure Bioscience||Disinfectant and method of use|
|US7803407||Jun 19, 2003||Sep 28, 2010||Pure Bioscience||Disinfectant and method of making|
|US8399028||Aug 14, 2008||Mar 19, 2013||Exciton Technologies Inc.||Antimicrobial silver solutions|
|US8591730||Jul 28, 2010||Nov 26, 2013||Siemens Pte. Ltd.||Baffle plates for an ultraviolet reactor|
|US8652336||Jun 5, 2007||Feb 18, 2014||Siemens Water Technologies Llc||Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water|
|US8741155||Jan 17, 2011||Jun 3, 2014||Evoqua Water Technologies Llc||Method and system for providing ultrapure water|
|US8753522||Jan 17, 2011||Jun 17, 2014||Evoqua Water Technologies Llc||System for controlling introduction of a reducing agent to a liquid stream|
|US8877067||May 25, 2012||Nov 4, 2014||Evoqua Water Technologies Llc||Method and arrangement for a water treatment|
|US8961798||Jan 17, 2011||Feb 24, 2015||Evoqua Water Technologies Llc||Method for measuring a concentration of a compound in a liquid stream|
|US8986606||May 26, 2009||Mar 24, 2015||Kemira Oyj||Chemistry for effective microbe control with reduced gas phase corrosiveness in pulp and paper processing systems|
|US9175489||Mar 21, 2013||Nov 3, 2015||Ronald James Turnbow||Water management system|
|US9365435||Jan 17, 2011||Jun 14, 2016||Evoqua Water Technologies Llc||Actinic radiation reactor|
|US9365436||Jan 17, 2011||Jun 14, 2016||Evoqua Water Technologies Llc||Method of irradiating a liquid|
|US9725343||Jun 16, 2014||Aug 8, 2017||Evoqua Water Technologies Llc||System and method for measuring and treating a liquid stream|
|US9764968||Mar 8, 2013||Sep 19, 2017||Evoqua Water Technologies Llc||Method and system for providing ultrapure water|
|US20030038277 *||Aug 9, 2001||Feb 27, 2003||Roy Martin||Calcium hypochlorite of reduced reactivity|
|US20030160004 *||Feb 26, 2002||Aug 28, 2003||Roy Martin||Free radical generator and method|
|US20030160005 *||Feb 26, 2002||Aug 28, 2003||Roy Martin||Enhanced air and water purification using continuous breakpoint halogenation with free oxygen radicals|
|US20030178374 *||Mar 20, 2002||Sep 25, 2003||Innovative Medical Services||Process for treating water|
|US20030198689 *||May 9, 2003||Oct 23, 2003||Innovative Medical Services||Disinfectant and method of making|
|US20040224088 *||Jun 15, 2004||Nov 11, 2004||United States Filter Corporation||Calcium hypochlorite of reduced reactivity|
|US20050109709 *||Oct 22, 2004||May 26, 2005||Usfilter Corporation|
|US20050202066 *||Aug 27, 2004||Sep 15, 2005||Arata Andrew B.||Silver dihydrogen citrate compositions comprising a second antimicrobial agent|
|US20050211612 *||Mar 25, 2004||Sep 29, 2005||Mattson Roy W Jr||Water suction purification device|
|US20050274624 *||Jun 19, 2003||Dec 15, 2005||Innovative Medical Services||Disinfectant and method of making|
|US20060051430 *||Sep 7, 2004||Mar 9, 2006||Arata Andrew B||Silver dihydrogen citrate compositions|
|US20060100273 *||Dec 8, 2005||May 11, 2006||Pure Bioscience||Anhydrous silver dihydrogen citrate compositions|
|US20060115440 *||Jun 3, 2005||Jun 1, 2006||Arata Andrew B||Silver dihydrogen citrate compositions|
|US20060188584 *||Apr 20, 2006||Aug 24, 2006||Arata Andrew B||Composition and process for treating acne|
|US20070185350 *||Mar 27, 2007||Aug 9, 2007||Arata Andrew B||Anhydrous silver dihydrogen citrate compositions|
|US20070212425 *||Mar 7, 2007||Sep 13, 2007||Barna Ivan J||Cidal formulations and methods of use|
|US20070269530 *||Aug 1, 2007||Nov 22, 2007||Pure Bioscience||Disinfectant and method of making|
|US20080023412 *||Sep 4, 2007||Jan 31, 2008||Engineered Solutions, Inc.||Portable tank wastewater treatment system and method|
|US20080185335 *||May 19, 2005||Aug 7, 2008||Holt Karl K||Septic System Remediation Method and Apparatus|
|US20080245738 *||Jan 11, 2008||Oct 9, 2008||Siemens Water Technologies Corp.||Method and system for providing ultrapure water|
|US20080319062 *||Sep 4, 2008||Dec 25, 2008||Arata Andrew B||Disinfectant and method of use|
|US20090099257 *||Dec 19, 2008||Apr 16, 2009||Arata Andrew B||Composition and process for treating acne|
|US20090291023 *||May 26, 2009||Nov 26, 2009||Mark Nelson||Chemistry for Effective Microbe Control with Reduced Gas Phase Corrosiveness in Pulp & Paper Processing Systems|
|US20100012593 *||Sep 4, 2009||Jan 21, 2010||Arata Andrew B||Process for treating water|
|US20100040699 *||Aug 14, 2008||Feb 18, 2010||Exciton Technologies Inc.||Antimicrobial silver solutions|
|US20100173018 *||Dec 9, 2009||Jul 8, 2010||Buckman Laboratories International, Inc.||Microbicidal Compositions Including Activated Nitrogenous Compound and 1,4-Bis(Bromoacetoxy)-2-Butene, and Methods Of Using The Same|
|US20100200502 *||Mar 30, 2010||Aug 12, 2010||Holt Karl K||Septic system remediation method and apparatus|
|US20110009484 *||Jul 12, 2010||Jan 13, 2011||Pure Bioscience||Disinfectant and method of making|
|US20110024365 *||Jul 28, 2010||Feb 3, 2011||Zhee Min Jimmy Yong||Baffle plates for an ultraviolet reactor|
|US20110209530 *||Jan 17, 2011||Sep 1, 2011||Siemens Water Technologies Corp.||Method for measuring a concentration of a compound in a liquid stream|
|US20110210048 *||Jan 17, 2011||Sep 1, 2011||Siemens Water Technologies Corp.||System for controlling introduction of a reducing agent to a liquid stream|
|US20110210077 *||Jan 17, 2011||Sep 1, 2011||Siemens Water Technologies Corp.||Method and system for providing ultrapure water|
|US20110210266 *||Jan 17, 2011||Sep 1, 2011||Siemens Water Technologies Corp.||Method of irradiating a liquid|
|US20110210267 *||Jan 17, 2011||Sep 1, 2011||Siemens Water Technologies Corp.||Actinic radiation reactor|
|CN102036921B *||May 26, 2009||Jan 20, 2016||凯米罗总公司||在纸浆和纸处理系统中用于以气相腐蚀性的降低有效控制微生物的化学作用|
|EP1044608A1 *||Mar 31, 1999||Oct 18, 2000||Altinco, S.L.||A phtosanitary product comprising quaternary ammonium salts as enhancers|
|WO2009143511A1 *||May 26, 2009||Nov 26, 2009||Kemira Oyj||Chemistry for effective microbe control with reduced gas phase corrosiveness in pulp & paper processing systems|
|WO2010080305A3 *||Dec 9, 2009||May 19, 2011||Buckman Laboratories International, Inc.||Microbicidal compositions including activated nitrogenous compound and 1,4-bis (bromoacetoxy)-2-butene, and methods of using the same|
|U.S. Classification||210/755, 210/764, 422/37, 422/28, 210/760|
|International Classification||A01N59/20, C02F1/50, C02F1/78, C02F1/76, A01N33/12|
|Cooperative Classification||A01N59/20, C02F1/50, A01N33/12, C02F1/78, C02F2103/42, C02F1/76|
|European Classification||A01N33/12, A01N59/20, C02F1/50, C02F1/78, C02F1/76|
|Jun 25, 1993||AS||Assignment|
Owner name: OLIN CORPORATION, CONNECTICUT
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GAY, WALTER A.;SANDEL, BONNIE B.;CARNEY, JAYNE F.;REEL/FRAME:006600/0467
Effective date: 19930623
|Jul 26, 1998||LAPS||Lapse for failure to pay maintenance fees|
|Oct 6, 1998||FP||Expired due to failure to pay maintenance fee|
Effective date: 19980729